The synthesis of nitrosyl-thiocarbonyl complexes of osmium

M. Herberhold; A. F. Hill; N. McAuley; W. R. Roper

doi:10.1016/S0022-328X(00)99663-3

The synthesis of nitrosyl-thiocarbonyl complexes of osmium

M. Herberhold^*, A. F. Hill, N. McAuley, W. R. Roper

^*Corresponding author for this work

Research School of Chemistry

Research output: Contribution to journal › Article › peer-review

25 Citations (Scopus)

Abstract

Two procedures for the conversion of coordinated CS₂ into CS ligands are described involving the intermediacy of either η²-carbonsulphide-telluride or hydridodithiomethoxycarbonyl complexes. The CS₂ ligand in OsCl(NO)(CS₂)(PPh₃)₂ is readily methylated to provide cationic dithiomethoxycarbonyl-containing complexes, which upon reduction with sodium hydrotelluride and sodium tetrahydroborate give OsX(NO)(CS)(PPh₃)₂ (X = Cl, I) and OsH₂ (CS₂Me)(NO)(PPh₃)₂, respectively. The latter reacts with electrophilic reagents (HCl, HI, I₂) to give OsX(NO)(CS)(PPh₃)₂, the halide of which is labile and is easily extracted by silver salts, allowing coordination of neutral ligands and providing the cations [Os(NO)(CS)(PPh₃)₂L]⁺ (L = CO, PPh₃). OsH₂(CS₂Me)(NO)(PPh₃)₂ and OsI(NO)(CS)(PPh₃)₂ react with an excess of I₂ to give the ionic product [OsI₂(NO)(CS)(PPh₃)₂]⁺I₃^-.

Original language	English
Pages (from-to)	95-106
Number of pages	12
Journal	Journal of Organometallic Chemistry
Volume	310
Issue number	1
DOIs	https://doi.org/10.1016/S0022-328X(00)99663-3
Publication status	Published - 12 Aug 1986

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title = "The synthesis of nitrosyl-thiocarbonyl complexes of osmium",

abstract = "Two procedures for the conversion of coordinated CS2 into CS ligands are described involving the intermediacy of either η2-carbonsulphide-telluride or hydridodithiomethoxycarbonyl complexes. The CS2 ligand in OsCl(NO)(CS2)(PPh3)2 is readily methylated to provide cationic dithiomethoxycarbonyl-containing complexes, which upon reduction with sodium hydrotelluride and sodium tetrahydroborate give OsX(NO)(CS)(PPh3)2 (X = Cl, I) and OsH2 (CS2Me)(NO)(PPh3)2, respectively. The latter reacts with electrophilic reagents (HCl, HI, I2) to give OsX(NO)(CS)(PPh3)2, the halide of which is labile and is easily extracted by silver salts, allowing coordination of neutral ligands and providing the cations [Os(NO)(CS)(PPh3)2L]+ (L = CO, PPh3). OsH2(CS2Me)(NO)(PPh3)2 and OsI(NO)(CS)(PPh3)2 react with an excess of I2 to give the ionic product [OsI2(NO)(CS)(PPh3)2]+I3-.",

author = "M. Herberhold and Hill, {A. F.} and N. McAuley and Roper, {W. R.}",

year = "1986",

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doi = "10.1016/S0022-328X(00)99663-3",

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T1 - The synthesis of nitrosyl-thiocarbonyl complexes of osmium

AU - Herberhold, M.

AU - Hill, A. F.

AU - McAuley, N.

AU - Roper, W. R.

PY - 1986/8/12

Y1 - 1986/8/12

N2 - Two procedures for the conversion of coordinated CS2 into CS ligands are described involving the intermediacy of either η2-carbonsulphide-telluride or hydridodithiomethoxycarbonyl complexes. The CS2 ligand in OsCl(NO)(CS2)(PPh3)2 is readily methylated to provide cationic dithiomethoxycarbonyl-containing complexes, which upon reduction with sodium hydrotelluride and sodium tetrahydroborate give OsX(NO)(CS)(PPh3)2 (X = Cl, I) and OsH2 (CS2Me)(NO)(PPh3)2, respectively. The latter reacts with electrophilic reagents (HCl, HI, I2) to give OsX(NO)(CS)(PPh3)2, the halide of which is labile and is easily extracted by silver salts, allowing coordination of neutral ligands and providing the cations [Os(NO)(CS)(PPh3)2L]+ (L = CO, PPh3). OsH2(CS2Me)(NO)(PPh3)2 and OsI(NO)(CS)(PPh3)2 react with an excess of I2 to give the ionic product [OsI2(NO)(CS)(PPh3)2]+I3-.

AB - Two procedures for the conversion of coordinated CS2 into CS ligands are described involving the intermediacy of either η2-carbonsulphide-telluride or hydridodithiomethoxycarbonyl complexes. The CS2 ligand in OsCl(NO)(CS2)(PPh3)2 is readily methylated to provide cationic dithiomethoxycarbonyl-containing complexes, which upon reduction with sodium hydrotelluride and sodium tetrahydroborate give OsX(NO)(CS)(PPh3)2 (X = Cl, I) and OsH2 (CS2Me)(NO)(PPh3)2, respectively. The latter reacts with electrophilic reagents (HCl, HI, I2) to give OsX(NO)(CS)(PPh3)2, the halide of which is labile and is easily extracted by silver salts, allowing coordination of neutral ligands and providing the cations [Os(NO)(CS)(PPh3)2L]+ (L = CO, PPh3). OsH2(CS2Me)(NO)(PPh3)2 and OsI(NO)(CS)(PPh3)2 react with an excess of I2 to give the ionic product [OsI2(NO)(CS)(PPh3)2]+I3-.

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AN - SCOPUS:0010961431

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IS - 1

ER -

The synthesis of nitrosyl-thiocarbonyl complexes of osmium

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